Physical properties

ABSTRACT

A LIQUID POLYSULFIDE POLYMER SEALANT COMPOSITION FOR SEALING GLASS TO METAL HAVING GREATLY IMPROVED ADHESION STABILITY WHEN EXPOSED TO ULTRAVIOLET RADIATION OR SUNLIGHT TRANSMITTED THROUGH GLASS AND GREATLY IMPROVED PENETROMETER CURE AND ADHESION RATE PROPERTIES IS OBTAINED BY USE OF HYDROQUINONE AND QUINONE ULTRAVIOLET RADIATION ADHESION STABILIZERS AND QUATERNARY AMMONIUM CHLORIDE CURING AND ADHESION RATE REGULATORS, QUINONE AND COMPOUNDS HAVING THE FORMULA   1,4-DI(R-O-),3,5-DI(R-)BENZENE   WHERE R REPRESENTS H OR ALKYL GROUPS HAVING 1-6 CARBON ATOMS, E.G. HYDROQUINONE AND P-METHOXY PHENOL, ARE EFFECTIVE ADDITIVES FOR PREVENTING LOSS OF COHESIVE STRENGTH OR LOSS OF ADHESION OF CURED POLYSULFIDE POLYMER COMPOSITIONS TO GLASS WHERE THE SEALANT/GLASS INTERFACE IS EXPOSED TO ULTRAVIOLET RADIATION, INCLUDING SUNLIGHT. HOWEVER, THE ADDITION OF THESE ADHESION STABILIZERS HAVE AN ADVERSE EFFECT ON QUICK ADHESION AND CURING RATE OF THE SEALANT, THEREFORE, THE ADDITION OF CURING AND ADHESION RATE REGULATORS IS REQUIRED. IMPROVED QUICK ADHESION AND CURE RATE PROPERTIES ARE OBTAINED BY THE USE OF QUATERNARY AMMONIUM CHLORIDES REPRESENTED BY THE FORMULA   (R-N(+)(-CH3)2-CH2-)BENZENE CL(-)   WHERE R REPRESENTS AN ALKYL HAVING 8 TO 24 CARBON ATOMS (AND QUATERNARY AMMONIUM CHLORIDES REPRESENTED BY THE FORMULA   (H-(O-CH(-R)-CH2)N-O-N(+)(-C3H5)(-C8H17)-CH2-)BENZENE   CL(-)   WHERE R&#39;&#39; REPRESENTS HYDROGEN OR METHYL AND N IS A NUMBER FROM 3 TO 5).

United States Patent Office Re. 27,880 Reissued Jan. 8, 1974 Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE A liquid polysulfide polymer sealant composition for sealing glass to metal having greatly improved adhesion stability when exposed to ultraviolet radiation or sunlight transmitted through glass and greatly improved penetrometer cure and adhesion rate properties is obtained by use of hydroquinone and quinone ultraviolet radiation adhesion stabilizers and quaternary ammonium chloride curing and adhesion rate regulators.

Quinone and compounds having the structure R OR where R represents H or alkyl groups having 1-6 carbon atoms, e.g. hydroquinone and p-methoxy phenol, are effective additives for preventing loss of cohesive strength or loss of adhesion of cured polysulfide polymer compositions to glass where the sealant/ glass interface is exposed to ultraviolet radiation, including sunlight. However, the addition of these adhesion stabilizers have an adverse effect on quick adhesion and curing rate of the sealant. Therefore, the addition of curing and adhesion rate regulators is required.

Improved quick adhesion and cure rate properties are obtained by the use of quaternary ammonium chlorides represented by the formula where R represents an alkyl having 8 to 24 carbon atoms [and quaternary ammonium chlorides represented by the formula where R represents hydrogen or methyl and n is a number from 3 to BACKGROUND OF THE INVENTION Field of the invention Description of the prior art Many SH terminated organic polymers are known in the art. Of particular interest to the practice of the present invention are liquid polythiol polymers having various backbones, such as hydrocarbon, alkylene polysulfide,

polyether, and polyurethane. SH terminated liquid polysulfide polymers are of most interest herein.

SH terminated polysulfide polymers are characterized by the fact that they have recurring polysulfide linkages between organic radicals having at least two primary carbon atoms for connection to disulfide linkages. Thus, for example, disulfide polymers have a general structure corresponding to the formula HStRSS-hRSH in which the Rs are organic polyvalent radicals, preferably predominantly divalent alkylene oxahydrocarbon or thiahydrocarbon radicals such as diethyl formal radicals, and n is a number greater than one, which may vary from a relatively small number in the case of liquid polymers having a molecular weight of about 500 to 25,000, e.g., about 3 to where R is to a relatively large number in the case of solid polymers which may have a molecular weight of about 100,000 to several million. The low molecular weight polysulfide polymers, e.g., 500 to 25,000, are normally liquids at 25 C. and are preferably formed by reaction of an organic dihalide with a backbone corresponding to R with an inorganic polysulfide, such as Na S it usually being greater than two. Solid organic polysulfide polymers are produced thereby which may then be split according to the method of Patrick and Ferguson in US. 2,466,963 to provide liquid polythiol polymers. The present invention concerns the use of adhesion stabilizers such as quinone and hydroquinone and curing and adhesion rate regulators such as quaternary ammonium chloride in water activated polysulfide sealant compositions resulting in unexpected improved adhesion stability of the cured polymer to glass and other substrates when exposed to ultraviolet radiation through the substrate while improving quick adhesion and fast curing rates.

Various adhesion additives and primers have been used to improve the adhesion of the polysulfide compositions to the various substrates, when necessary. Suitable adhesion additives include, for example, phenolic resins; polyvinyl acetate; alkoxy silanes of various types including mercapto and amino derivatives thereof, such as described in US. Pats. 3,297,473 and 3,312,669; and alkoxy silane terminate polysulfide polymers, which are particularly useful as adhesion additives for the high rank polysulfide polymers as described in US. 3,476,826. Various commercially available primers have also been used with polysulfide polymers, silicoues, vinyl resins, fnrane resins and others. Commercially, adhesion additives are usually preferred to primers because of the simplicity of application.

Although the above-mentioned adhesion additives and primers are useful for certain applications, they are not always capable of maintaining the adhesion of cured polysulfide polymer compositions to glass which is exposed to ultraviolet radiation or sunlight with the glass facing the light source. Using black formulations cured with calcium peroxide, for example, there is almost complete adhesive failure at the sealant/ glass interface within 1 or 2 days. Compositions containing other curing agents vary in their susceptibility to ultraviolet light, but all show a similar tendency in different degrees. There is no loss of adhesion of polysulfide sealants properly bonded to glass when sunlight strikes the sealant surface rather than being transmitted to the sealant/glass interface through the glass.

The problem of light striking the glass/sealant interface arises, for example, in the case of automobile windshields and the thermopane windows exposed to sunlight or in the case of glass enclosed structures exposed to ultraviolet light, as might occur in research or hospital laboratories. Thus, ordinarily, polysulfide sealant formula tions, particularly black or colored formulations, would not be suitable for such uses involving prolonged exposure to light.

No prior art is known to the applicant which incorporates the quaternary ammonium chloride into water activated polysulfide sealant compositions. The use of cationic alkyl substituted quaternary ammonium salts is described in Rike, US. 2,776,010 issued Jan. 1, 1957. However, these quaternary ammonium salts are used as emulsifying agents in oil emulsion cements comprising portland cement, liquid hydrocarbon oil and water to form a pumpable slurry for sealing porous earth in oil wells. Therefore, the latter system would be completely unsuitable for attaining the objectives of the present invention.

SUMMARY OF THE INVENTION Thus it is an object of the invention to provide liquid polysulfide polymer compositions, particularly wateractivated calcium peroxide-containing liquid polysulfide compositions, which have improved adhesion, in the cured state, to glass substrates which are exposed to ultraviolet radiation or sunlight transmitted through the glass. This object is accomplished by incorporating in the liquid polysulfide polymers composition, prior to cure, as an adhesion stabilizer an adhesion stabilizing amount of (1) a compound having the structure R OR where the R's may be H or a lower alkyl group having 1-6 carbon-atoms, or (2) quinone. The amount of adhesion stabilizer may range from 0.10 part to parts per 100 parts by weight of the liquid polysulfide polymer.

The adhesion stabilizer may be incorporated at the other ingredients in the sealant formulation or it may be added alone to the liquid polymer beforehand, since this has no deleterious eifect on the polymer during storage and does not atfect the ultimate stabilizing effect in the cured composition.

Another object of the invention is directed to improveing quick adhesion, curing rate and the range of water concentration for cure activation in the water-activated liquid polysulfide compositions especially since the ultraviolet radiation adhesion stabilizers incorporated in this invention tend to retard quick adhesion and curing rates. This object is accomplished by incorporating in the liquid polysulfide polymer composition, prior to cure, as a curing and adhesion rate regulator, a regulating amount of [(1)] a quaternary ammonium chloride represented by the structure atoms [or (2) a quaternary ammonium chloride represented by the structure where R represents hydrogen or methyl and n is a number from 3 to 5].

The improved liquid polysulfide polymer composition of the invention can be rapidly cured for sealant applications, such as for automotive sealing and glazing, automotive windshield sealing and architectual sealing and glazing.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polymers useful in the practice of the present invention are liquid polysulfide polymers such as described in U.S. 2,466,963. These have the general formula HS(RSS),,RSH where R is a divalent aliphatic organic radical, which may contain 0 or S in the carbon chain and n has a value such that the molecular weight is between 500 and 25,000. They are viscous liquids having viscosities within the range of 300 to 150,000 poises at 25 C. The commercially important liquid polymers of this type are particularly described in articles by Fettes and Jorczak, published in Industrial and Engineering Chemistry," vol. 42, p. 2217 (1950), and vol. 43, p. 324 (1951). They are generally prepared from bis-betachlorocthyl formal and are essentially composed of recurring (-SCH CH -OCH OCH CH S) groups and have free mercapto terminals through which they may be cured to form a solid elastomer. In the manufacture of these commercial polymers, a small percentage of trichloropropane is commonly mixed with the bis-betachloroethyl formal to provide a slightly cross-linked structure upon cure. Particularly, commercially valuable polymers include those having preferably recurring groups, such as bis(ethyleneoxy) methane, bis(butyleneoxy)methane, bis(ethylene)oxy, and bis(butylene)oxy and an average molecular weight of approximately 1,000 to 10,000 and preferably 3,500 to 8,000.

The liquid polysulfide polythiol polymers may be cured to solid elastomers with a large variety of organic and inorganic oxidative curing agents, such as described in an article by Interscience Publishers, dated 1962, entitled Polyethers Part III Polyalkylene Sulfides and Other Polythioethers published in vol. XIII of the High Polymer Series of pp. 164-172. Certain curing agents are particularly useful in commercial sealant formulations as dormant curing agents which are activated by water at the time the cure is desired. Such curing agents include, for example, calcium peroxide, barium peroxide, lithium peroxide, lead dioxide, manganese dioxide and calcium orthoplumbate. Although lead peroxide cures are accelerated by water, lead peroxide is so active even inextremely dry compositions that it cannot be considered a dormant curing agent suitable for use in one-package systems. Lead peroxide and calcium orthoplumbate cured polysulfide compositions show an increase in cohesive strength by inclusion of the stabilizers of the present invention although they have better resistance to loss of adhesion than those containing some of the other curing agents listed above, particularly calcium peroxide.

The ultraviolet radiation adhesion stabilizers and the curing and adhesion rate regulators described herein are effective with liquid polysulfide polymer sealant compositions containing the usual additives used in commercial applications such as fillers, pigments, plasticizers, surfactants, accelerators, retarders, adhesion additives, etc. The use of the conventional primers normally used with any particular formulation is also recommended.

The adhesion stabilizers may be represented by quinone and a composition having the formula where R represents H or an alkyl containing from 1 to 6 carbon atoms. For example, R may be hydrogen, methyl, ethyl, propyl, butyl, penta, and hm, The preferred adhesion stabilizers are hydroquinone, p-quinone, p-methoxyphenol, and p-dimethoxybenzene.

The adhesion stabilizers contained in the sealant composition may be present in amounts from about 0.1 to 5 parts by weight per 100 parts by weight of the liquid polysulfide polymer, preferably 0.1 to 2 parts by weight.

The quaternary ammonium chloride curing and adhesion rate regulators may be represented by the formula iii Jfl -12] Q-CihlZO on, 110.21 (:1

where R represents hydrogen or methyl and n is a number from 3 to 5, preferably R is hydrogen and n is 4].

The preferred quaternary ammonium chlorides are myristyl dimethyl benzyl ammonium chloride [and 1,4,7 ,10- tetraoxa-dodecan-lZ-ol ethyl octyl ammonium chloride].

The cationic quaternary ammonium chloride sold under the trademark Katapone VV328 with a molecular weight of 476.5, specific gravity of 0.99 and with 64.79% carbon, 10.75% hydrogen, 13.70% oxygen, 3.31% nitrogen and 7.45% chlorine is also preferred.

The quaternary ammonium chloride curing and adhesion rate regulators contained in the sealant composition may be present in amounts from about 0.1 to 1 part by weight per 100 parts by weight of the liquid polythiol polymer, preferably 0.2 to 0.3 part by weight.

The composition also includes (1) alkaline earth metal oxide compounds, particularly, calcium oxide, barium oxide, and magnesium oxide, (2) plasticizers, such as, chlorinated hydrocarbons, (3) fillers, (4) curing accelerators, such as, tertiary amines, more particularly trimethylamine, triethylamine, N(tripropylamine) and tri-nbutylamine, (5) moisture activated curing agents and (6) other ingredients usually included in sealant formulations.

In the sealant composition, all the ingredients are simply stirred or mixed together in the absence of water to homogenize the composition. The composition can be stored or shipped in this form in sealed packages.

To form the curable sealant composition, the sealant ingredients are simply mixed with from 1 to 2.5% water by weight based on the total weight of the composition, or more preferable 1.5 to 2% water by weight. The composition is ready to apply to a substrate, such as, glass, metal, plastics and, more particularly automobile windshields. Setting begins within a few minutes in the presence of water and curing is substantially completed in less than 4 hours in most cases.

In order to point out more fully the invention in its practical aspects, the following illustrative examples are given of the practice of the invention for preparing the sub-combinations and combinations of the ingredients used in their various phases.

The invention is illustrated by means of a representative, commercially available -SH terminated LP-32 liquid polysulfide polymer. The LP-32 polymer has the formula a molecular weight of 4,000, and 0.5% of branching in the side chains. A commercially available LP-Z liquid polysulfide polymer has a similar formula and molecular weight as the LP-32 liquid polysulfide polymer but dilfers in having 2% branching in the side chains. However, LP-32 polymer yields cured elastomers having softer body and greater elongation than does LP-2 polymer which could also be used in its composition.

While the invention is illustrated with the LP-32 liquid polysulfide polymer, it is to be understood that the invention may be practiced with other polythiol reactants.

EXAMPLES 1-19 In Examples 1-19, the ingredients of the formulations except the water, were hand mixed together in a suitable container and dispersed on a 3 roll paint mill. The water was then mixed with an electrically driven mixing blade for 3 to 5 minutes. The sealant was used to bond together strips of primed enameled autobody metal and glass surfaces previously primed with a silane primer. After an overnight cure at room temperature, the glass/sealant interfaces were exposed to ultraviolet radiation from various sources transmitted through the glass. The shear adhesion of the sealant to the glass was tested by applying sufficient material to 0.25" x 1" x 4" glass plates precoated with primer to provide a bond area of 1 sq. inch by Vs" thickness when mated with a 0.090" x 1" x 3" enameled steel panel precoated with primer. The panels were pulled apart by a standard testing machine having a jaw separation rate of 1" per minute.

The primer used on the glass was a commercially available aminoalkyl silicone primer. However, a chlorinated rubber urethane primer containing approximately 5% to 10% solids was used also as a top coat for the aminoalkyl silicone primer.

The basic formulation used to test the adhesion stabilizers contained one hundred parts of a liquid polysulfide polymer (CzHqOCHgQCzHq 33C2 3O C2H4SH having 0.5% cross-linking, and the following ingredients by weight:

Chlorinated biphenyl plasticizer 54% Cl (Aroclor 1254) 40 CaO 5 CaO; (60%) 8 Triethylamine 0.5 Sterling MT carbon black 50 Sterling R carbon black 20 Toluene 3.5 Water 3 The identity of the stabilizers tested in the examples is as follows:

Stabilizer Chemical name Structure Shear adhesion, p.s.i. after outside exposure of- Sta- Sea- Ex. nlltzer Pbw. son 7 days l4 days 30 days Control W 3% CF 43 AF 60 AF 0. 5 W 68 MPF 158 MPF 73 MPF 0.6 W 88 MPF 131 MPF 73 MPF 0.5 W 238 OF 176 OF 270 CF 0. 6 S 183 OF 215 OF 214 CF 1.0 S 206 OF 222 OF 220 CF 2. 0 S 176 OF 210 OF 220 OF 0. 26 S 215 OF 240 OF 245 OF 0.6 W 264 OF 116 SCF, PF 2133 CF One of the most eflective stabilizers, hydroquinone (HQ) was tested at various levels using the same sealant formulation and primers as in Examples 1-9. The sealant/glass interfaces were exposed to outside radiation (late summer, northeast US.) and to ultraviolet radiathe acceptable curing rate and quick adhesion properties of the sealant.

The penetrometer cure rate test indicates the time necessary for the sealant to cure. As the sealant approaches a completely cured state the penetrometer tion from the carbon arc in an Atlas Weatherometer. needle will penetrate less into the sealant. Therefore, the Model XW.Shear adhesion test results were as folsmaller the distance, in mm., the needle has penetrated lows: the material as shown in Examples 20-27 the more completely the sealant has cured. When the needle fails to Sham. adhesion, PM" weathemmeter o penetrate the sealant a complete cure has been obtained. E Ego. Oudtside Exposure In the quick adhesion test, beads of the sealant are p 14 ays days 500 placed on specially prepared test panels. These beads are lg).-- c 22 i238? gag? 3E2 205 60% CF 170 60% CF peeled from the panels or substrates at predetermined 1:: 195 OF 200 OF 244 CF 5.388%: times. When the beads are peeled from the substrates the 13- 2.0 223 OF 238GB 24.2 CF CF 215 CF most desirable situation is for the head to exhibit a cohesive failure resulting in a portion of the bead remaining Hydmquinone was also tested as a stabilizm. in the on the substrate. The most undesirable situation is for same sealant formulation except that the curing agent was the bead .When Pulled y the animate to exhlblt changfid as follows: an adhesion failure resulting in no port1on of the bead remaining on the substrate. Another situation which 15 also undesirable is the situation where the bead when Parts by peeled from the substrate leaves only a very thin film. Example Curing agent weight This indicates that there has been some cohesion failure i2: hgi ig g i g ggg g in the bead. However, it also indicates some adhesion Calcium orthoplumbate (0aiPb0i) 20 failure which [5 certainly undeslrable.

The penetrometer cure rate test is conducted by placing a test specimen /2" thick onto a S" x 10" glass panel. The test s cimen is allowed to cure at 77 F. shear ;i}3 .%3?1 for 1 hour. The penetrometer needle as described in ASTM-DS is adjusted so that it just touches the surface Sewn Mays M days aodays of the test specimen, Then a 50 gram loaded needle is }g---- g g a 2 kg; ggg fg gg g: applied for 5 seconds as described in ASTM-D5 and w o 43 0F the penetration of the needle into the specimen is rew :2: 13g 8g corded in mm.s. This test was conducted in Examples 1 on I: j OF 20-27 after the first hour and at A hour intervals thereafter for 7 hours and the results recorded. The above examples illustrate the effect of hydrog ;.f i f g ggg gg ggg g igg ggg ggi :2; g gggz ifig the coheswe strength of cured Polycoating it with a white acrylic body lacquer using the EXAMPLES 2047 0 flow coat process. The acrylic lacquer was then coated with a chlorinated rubber urethane primer cotaimng The room temperature penetrometer cure rate and the approximately 5% to 10% solids. Also used in the test qualitative quick adhesion properties of curable liquid is 1 primed glass 5" x 10" panel. The primer used on polysulfide sealant compositions containing from 0 to the glass was a commercially available aminoalkyl sili- 2.0 parts by weight of hydroquinone per 100 parts of LP- cone primer. However, a chlorinated rubber urethane 32, -SH terminated liquid polysulfide polymer and from primer containing approximately 5% to 10% solids was 0 to 0.75 part by weight of myristyl dimethyl benzyl used also as a top coat for the aminoalkyl silicone ammonium chloride per 100 parts of the liquid polyprimer. Nine beads of the test material are applied to the sulfide polymer is shown by the following examples. glass and steel panels at 77 F. After application of In each example the room temperature curable sealant the sealant beads, all test panels are allowed to cure at composition was prepared by homogeneously mixing to- 77 F. for 1 hour, then immersed in cold water for 10 gether the listed ingredients at room temperatures about minutes and removed. One head is immediately peeled 70 to 75 F., then adding 1.7% total composition weight from both the glass and steel panels. A bead is reof water to activate the system. moved each hour thereafter for 7 hours then a bead The curing rate and quick adhesion properties are is removed after 24 hours. Failure should occur within vital in sealants used in automobile windshield sealing the bead itself. This type of failure is cohesive failure applications. and is desirable. Adhesion failure is undesirable since Examples 20-27 illustrate that the addition of the ultrathe head would be completely pulling away from the violet adhesion stabilizer has an adverse eflect upon both substrate. This test was conducted in Examples 20-27 the curing rate and quick adhesion properties of the liquid and the results recorded. polysuliide sealants. However, these examples further The compositions as prepared and cured, and the illustrate that the addition of small amounts of the curphysical properties as found for the cured test pieces were ing and adhesion rate regulator, restores and improves as follows:

Example number 20 21 22 23 34 25 26 27 SH terminated polysultlde polymer (Thiolol LP-32) 100 100 100 100 100 100 100 100 Hydroqulnone (Tennessee Eastman Corp. 11-329 0 0 0.25 0.25 0.5 0.5 2.0 2.0 Myrlstyl dimethylbenzyl ammonium chloride (ONYX Chemical Company B'IG 100) 0 0.5 0.25 0. 0.5 1.0 0.25 0. 75 Chlorinated hydrocarbon plasticizer containing 54% Cl (Monsanto Co Aroelor1254) 40 40 40 40 40 40 40 40 'Iriethylarnine 0.5 0.5 0.5 0.5 0.5 as 0.5 0.5 Carbon black (Cabot Corp. Sterling MT) pigment" 50 50 50 50 50 50 5O 50 Carbon black (Cabot Corp. Sterling R) igment 20 20 20 20 20 20 20 20 Calcium peroxide (FMC Corp. Becco 60%) curing agent... 8 8 8 8 8 8 B 8 Caltlllim oxide 5 5 a 5 5 5 s 5 Toluene 8.5 3.5 3.5 3.5 3.5 3.5 5 3.5 Water (activator) 1.7% 0! total weight PHYSICAL PROPERTIES (a) Penetrcmeter cure rate, mm.

10 the group consisting of quinone and a composition having the formula Penetration (mm.) B

Example number 20 21 22 23 24 25 28 27 no OR 1e to is 1a 1e 1e 1e 1a is m 15.6 is 11.3 is 14.5 12.8 10 7.8 is

2:3 3:; 1g :1 I 3:: 10 wherein R represents H or alkyl having from i to 6 car- 2.3 2.; g-g g-i bon atoms, and a dispersing and penetrometer cure rate 1 5 improving amount of a curing and adhesive rate regulator 2-3 2-2 [selected from the group consisting of a] quaternary ammonium chloride represented by the formula (b) Quick adhesion Adhesion properties Example number 21 22 23 24 25 2o 27 C=Com lete cure. MO =Me umcure BC=Soit cure. VSC=Very soft cure. TF=Thlck film (remaining alter head is removed). VTF=Very thin film (remaining after head is removed). CF=Coheslon Failure. AF=Adhesion Failure.

We claim: Cm 1. A curable polysulfide polymer sealant composition containing a water activated curing system comprising in Pix-R 1 admixture: H:

( a terminated liquid Polysulfida P y wherein R represents an alkyl containing from 8 to 24 represented y the formula carbon atoms[, and a quaternary ammonium chloride HS(C2H4 O CH O C2H4 S 5) represented by the formula I C2H4-O CHgO C2H4-SH 4 1* N-O an 11-0 H 01- and having a molecular weight of 4,000 and from G P 0.5 to 2 percent branching in the side chains;

(b) from about 6 to 10 parts by weight per 100 parts where R is selected from the group consisting of hydrogen by weight of said polymer of calcium peroxide curing and methyl, and n is a number from 3 to 5]. agent; 3. A method as in claim 2 wherein the ultraviolet radia- (c) from about 0.1 to 5 parts by weight per 100 parts tion adhesion stabilizer is selected from the group conby weight of said polymer of hydroquinone adhesion sisting of hydroquinone, p-quinone, p-methoxyphenol and stabilizer; p-dimethoxybenzene.

(d) from about 0.1 to 1 part by weight per 100 parts [4. A method as in claim lwherein the quaternary amby weight of said polymer of myristyl dimethyl benmonium chloride is represented by the formula zyl ammonium chloride curing and adhesion rate regulator; g ck (e) from about 3 to 7 parts by weight per 100 parts 6 by weight of said polymer of calcium oxide;

(f) from about 30 to 50 parts by weight per 100 parts wherein R represents an alkyl containing from 8 to 24 by weight of said polymer of a chlorinated biphenyl carbons] plasticizer; 5. A method as in claim [4] 2 wherein the quaternary (g) from about 0.1 to 1 part by weight per 100 parts ammonium chloride is myristyl dimethyl benzyl amby weight of said polymer of tricthyl amine; monium chloride.

(h) from about 50 to 90 parts by weight of carbon [6. A method as in claim 2 wherein the quaternary black per 100 parts by weight of said polymer; and ammonium chloride is represented by the formula (i) a liquid carrier. can t 2. In a method for producing an improved ultraviolet l:

stabilized sealant composition for sealing glass to metal g Carin-O H C1- by admixing liquid polysulfide polymer, alkaline earth all" metal Oxide, chlorinated hydfoflafboll Plasticilef, fi wherein R is selected from the group consisting of hydroactivating amine, inorganic metal peroxide curing agent, gen and methyl, nd n i a number from 3 to 5.]

a liquid carrier, an activating amount of water wherein [7, A method as i cl im 6 wherein th quaternary the improvement comprises admixing an ultraviolet staammonium chloride is l,4,7,l0-tetraoxa-dodecan-l2-ol bilizing amount of an adhesion stabilizer selected from ethyl octyl ammonium chloride] 8. A method as in claim 2 wherein the liquid polysultide polymer is a SH terminated liquid polysulfide polymer represented by the formula 9. A method as in claim 2 wherein the curing agent is selected from the group consisting of calcium peroxide, barium peroxide, manganese dioxide, lithium peroxide, lead dioxide and calcium orthoplumbate.

10. In a method for producing an improved ultraviolet stabilized sealant composition for sealing glass to metal by admixing liquid polysulfide polymer, alkaline earth metal oxide, chlorinated hydrocarbon plasticizer, fillers, activating amine, inorganic metal peroxide curing agent, a liquid carrier, an activating amount of water wherein the improvement comprises admixing 0.1 to five parts by weight per 100 parts by Weight of liquid polysulfide polymer of ultraviolet radiation adhesion stabilizer selected from the group consisting of quinone and a composition having the formula,

where R is selected from the group consisting of H and an alkyl having from one to six carbon atoms.

11. A method as in claim 10 wherein the liquid polysulfide polymer is a SH terminated liquid polysulfide polymer represented by the formula References Cited The following references, cited by the Examiner, are of record in patented file of this patent or the original patent.

UNITED STATES PATENTS 2,325,152 7/1943 Sibley 26045.95 X 3,043,672 7/1962 Ecke et al. 26045.95 X 3,282,902 11/1966 Panek 260-37 R 3,413,261 11/1968 Schalin et al. 26045.7 R

LEWIS T. JACOBS, Primary Examiner US. Cl. X.R. 

